Synergistic fungicidal mixtures for fungal control in cereals

ABSTRACT

A fungicidal composition containing a fungicidally effective amount of a compound of Formula I-V and at least one fungicide selected from the group consisting of epoxiconazole, prothioconazole, azoxystrobin, pyraclostrobin, penthiopyrad, isopyrazam, bixafen, boscalid, prochloraz, and chlorothalonil provides synergistic control of selected fungi.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/249,479, filed Oct. 7, 2009, which is expresslyincorporated by reference herein.

FIELD OF THE INVENTION

This invention concerns a synergistic fungicidal composition containing(a) a compound of Formula I, II, III, IV or V and (b) at least onefungicide selected from the group consisting of epoxiconazole,prothioconazole, azoxystrobin, pyraclostrobin, penthiopyrad, isopyrazam,bixafen, boscalid, prochloraz, and chlorothalonil.

BACKGROUND OF THE INVENTION

Fungicides are compounds, of natural or synthetic origin, which act toprotect plants against damage caused by fungi. Current methods ofagriculture rely heavily on the use of fungicides. In fact, some cropscannot be grown usefully without the use of fungicides. Using fungicidesallows a grower to increase the yield and the quality of the crop, andconsequently, increase the value of the crop. In most situations, theincrease in value of the crop is worth at least three times the cost ofthe use of the fungicide.

However, no one fungicide is useful in all situations and repeated usageof a single fungicide frequently leads to the development of resistanceto that and related fungicides. Consequently, research is beingconducted to produce fungicides and combinations of fungicides that aresafer, that have better performance, that require lower dosages, thatare easier to use, and that cost less.

Synergism occurs when the activity of two or more compounds exceeds theactivities of the compounds when used alone.

SUMMARY OF THE INVENTION

It is an object of this invention to provide synergistic compositionscomprising fungicidal compounds. It is a further object of thisinvention to provide processes that use these synergistic compositions.The synergistic compositions are capable of preventing or curing, orboth, diseases caused by fungi of the classes Ascomycetes andBasidiomycetes. In addition, the synergistic compositions have improvedefficacy against the Ascomycete and Basidiomycete pathogens, includingleaf blotch and brown rust of wheat. In accordance with this invention,synergistic compositions are provided along with methods for their use.

DETAILED DESCRIPTION OF THE INVENTION

The present invention concerns a synergistic fungicidal mixturecomprising an fungicidally effective amount of (a) a compound of FormulaI, II, III, IV or V, and (b) at least one fungicide selected from thegroup consisting of epoxiconazole, prothioconazole, azoxystrobin,pyraclostrobin, penthiopyrad, isopyrazam, bixafen, boscalid, prochlorazand chlorothalonil.

Azoxystrobin is the common name for methyl(αE)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α-(methoxymethylene)benzeneacetate.Its fungicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Azoxystrobin controls a variety of pathogens atapplication rates between 100 and 375 grams/hectare (g/ha).

Bixafen is the common name forN-(3′,4′-dichloro-5-fluoro[1,1′-biphenyl]-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.Bixafen controls a variety of pathogens such as Septoria tritici andrust.

Boscalid is the common name for2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide. Its fungicidal activityis described in The Pesticide Manual, Fifteenth Edition, 2009. Boscalidprovides control of powdery mildews, Alternaria, Botrytis, Sclerotinia,Mycoshpaerella and Monilinia on fruit, turf, cereals, rape, peanuts andpotatoes.

Chlorothalonil is the common name for tetrachlorisophthalonitrile. Itsfungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Chlorothalonil controls a wide variety of pathogens atapplication rates between 1000 to 2500 g/ha.

Epoxiconazole is the common name forrel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiranyl]methyl]-1H-1,2,4-triazole.Its fungicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Epoxiconazole provides broad-spectrum fungicidal control,with preventative and curative action, of diseases caused byAscomycetes, Basidiomycetes and Deuteromycetes in cereals and sugarbeet.

Isopyrazam is the common name for3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide.Its fungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Isopyrazam provides control of Septoria and rusts inwheat, as well as Ramularia in barley.

Penthiopyrad is the common name forN-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide.Its fungicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Penthiopyrad provides control of rust and Rhizoctoniadiseases, as well as grey mold, powdery mildew and apple scab.

Prochloraz is the common name forN-propyl-N-[2,4,6-trichlorophenyoxy)ethyl]imidazole-1-carboxamide. Itsfungicidal activity is described in The Pesticide Manual, FifteenthEdition, 2009. Prochloraz provides control against a wide variety ofpathogens at application rates between 400 to 600 g a.i./ha.

Prothioconazole is the common name for2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione.Its fungicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Prothioconazole is used for control of diseases such aseyespot, Fusarium ear blight, leaf blotch, rust and powdery mildew byfoliar application in wheat, barley and other crops.

Pyraclostrobin is the common name for methyl[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]phenyl]methoxycarbamate.Its fungicidal activity is described in The Pesticide Manual, FourteenthEdition, 2006. Pyraclostrobin controls major plant pathogens, such asSeptoria tritici, Puccinia spp., Drechslera tritici-repentis andPyrenophora teres in cereals.

In the composition of this invention, the weight ratio of the compoundsof Formula I-V to epoxiconazole at which the fungicidal effect issynergistic lies within the range of between about 1:10 and about 10:1.The weight ratio of the compounds of Formula I-V to prothioconazole atwhich the fungicidal effect is synergistic lies within the range ofbetween about 1:10 and about 10:1. The weight ratio of the compounds ofFormula I-V to azoxystrobin at which the fungicidal effect issynergistic lies within the range of between about 1:10 and about 10:1.The weight ratio of the compounds of Formula I-V to pyraclostrobin atwhich the fungicidal effect is synergistic lies within the range ofbetween about 1:10 and about 10:1. The weight ratio of the compounds ofFormula I-V to penthiopyrad at which the fungicidal effect issynergistic lies within the range of between about 1:10 and about 10:1.The weight ratio of the compound of Formula I to isopyrazam at which thefungicidal effect is synergistic lies within the range of between about1:10 and about 10:1. The weight ratio of the compound of Formula I tobixafen at which the fungicidal effect is synergistic lies within therange of between about 1:10 and about 10:1. The weight ratio of thecompounds of Formula I-V to boscalid at which the fungicidal effect issynergistic lies within the range of between about 1:10 and about 10:1.The weight ratio of the compounds of Formula I-V to prochloraz at whichthe fungicidal effect is synergistic lies within the range of betweenabout 1:10 and about 10:1. The weight ratio of the compounds of FormulaI-V to chlorothalonil at which the fungicidal effect is synergistic lieswithin the range of between about 1:50 and 1:1.

The rate at which the synergistic composition is applied will dependupon the particular type of fungus to be controlled, the degree ofcontrol required and the timing and method of application. In general,the composition of the invention can be applied at an application rateof between about 65 grams per hectare (g/ha) and about 2300 g/ha basedon the total amount of active ingredients in the composition.Epoxiconazole is applied at a rate between about 30 g/ha and about 125g/ha and the compound of Formula I-V is applied at a rate between about35 g/ha and about 300 g/ha. Prothioconazole is applied at a rate betweenabout 50 g/ha and about 200 g/ha and the compound of Formula I-V isapplied at a rate between about 35 g/ha and about 300 g/ha. Azoxystrobinis applied at a rate between about 50 g/ha and about 250 g/ha and thecompound of Formula I-V is applied at a rate between about 35 g/ha andabout 300 g/ha. Pyraclostrobin is applied at a rate between about 50g/ha and about 250 g/ha and the compound of Formula I-V is applied at arate between about 35 g/ha and about 300 g/ha. Penthiopyrad is appliedat a rate between about 50 g/ha and about 300 g/ha and the compound ofFormula I-V is applied at a rate between about 35 g/ha and about 300g/ha. Isopyrazam is applied at a rate between about 30 g/ha and about125 g/ha and the compound of Formula I is applied at a rate betweenabout 35 g/ha and about 300 g/ha Bixafen is applied at a rate betweenabout 30 g/ha and about 125 g/ha and the compound of Formula I isapplied at a rate between about 35 g/ha and about 300 g/ha. Boscalid isapplied at a rate between about 50 g/ha and about 350 g/ha and thecompound of Formula I-V is applied at a rate between about 35 g/ha andabout 300 g/ha. Prochloraz is applied at a rate between about 50 g/haand about 450 g/ha and the compound of Formula I-V is applied at a ratebetween about 35 g/ha and about 300 g/ha. Chlorothalonil is applied at arate between about 100 g/ha and about 2000 g/ha and the compound ofFormula I-V is applied at a rate between about 35 g/ha and about 300g/ha.

The components of the synergistic mixture of the present invention canbe applied either separately or as part of a multipart fungicidalsystem.

The synergistic mixture of the present invention can be applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis,Bacillus subtilis strain QST713, benalaxyl, benomyl,benthiavalicarb-isopropyl, benzylaminobenzene-sulfonate (BABS) salt,bicarbonates, biphenyl, bismerthiazol, bitertanol, bixafen,blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole,bupirimate, calcium polysulfide, captafol, captan, carbendazim,carboxin, carpropamid, carvone, chlazafenone, chloroneb, chlorothalonil,chlozolinate, Coniothyrium minitans, copper hydroxide, copper octanoate,copper oxychloride, copper sulfate, copper sulfate (tribasic), cuprousoxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil,dazomet, debacarb, diammonium ethylenebis-(dithiocarbamate),dichlofluanid, dichlorophen, diclocymet, diclomezine, dichloran,diethofencarb, difenoconazole, difenzoquation, diflumetorim,dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinobuton,dinocap, diphenylamine, dithianon, dodemorph, dodemorph acetate, dodine,dodine free base, edifenphos, enestrobin, enestroburin, epoxiconazole,ethaboxam, ethoxyquin, etridiazole, famoxadone, fenamidone, fenarimol,fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil,fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate,fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph,fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates,GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalilsulfate, imibenconazole, iminoctadine, iminoctadine triacetate,iminoctadine tris(albesilate), iodocarb, ipconazole, ipfenpyrazolone,iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam,isotianil, kasugamycin, kasugamycin hydrochloride hydrate,kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb,mefenoxam, mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride,mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metconazole,methasulfocarb, methyl iodide, methyl isothiocyanate, metiram,metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate,oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, pentachlorophenyl laurate, penthiopyrad,phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin,polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassiumhydroxyquinoline sulfate, probenazole, prochloraz, procymidone,propamocarb, propamocarb hydrochloride, propiconazole, propineb,proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin,pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyriofenone, pyroquilon, quinoclamine, quinoxyfen,quintozene, Reynoutria sachalinensis extract, sedaxane, silthiofam,simeconazole, sodium 2-phenylphenoxide, sodium bicarbonate, sodiumpentachlorophenoxide, spiroxamine, sulfur, SYP-Z048, tar oils,tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram,zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp.,Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.,(RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, copperbis(3-phenylsalicylate), copper zinc chromate, cufraneb, cuprichydrazinium sulfate, cuprobam, cyclafuramid, cypendazole, cyprofuram,decafentin, dichlone, dichlozoline, diclobutrazol, dimethirimol,dinocton, dinosulfon, dinoterbon, dipyrithione, ditalimfos, dodicin,drazoxolon, EBP, ESBP, etaconazole, etem, ethirim, fenaminosulf,fenapanil, fenitropan, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos,isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride,myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, prothiocarb;prothiocarb hydrochloride, pyracarbolid, pyridinitril, pyroxychlor,pyroxyfur, quinacetol; quinacetol sulfate, quinazamid, quinconazole,rabenzazole, salicylanilide, SSF-109, sultropen, tecoram, thiadifluor,thicyofen, thiochlorfenphim, thiophanate, thioquinox, tioxymid,triamiphos, triarimol, triazbutil, trichlamide, urbacid, zarilamid, andany combinations thereof.

The compositions of the present invention are preferably applied in theform of a formulation comprising a composition of (a) a compound ofFormula I and (b) at least one fungicide selected from the groupconsisting of epoxiconazole, prothioconazole, azoxystrobin,pyraclostrobin, penthiopyrad, isopyrazam, bixafen, boscalid, prochloraz,and chlorothalonil, together with a phytologically acceptable carrier.

Concentrated formulations can be dispersed in water, or another liquid,for application, or formulations can be dust-like or granular, which canthen be applied without further treatment. The formulations are preparedaccording to procedures which are conventional in the agriculturalchemical art, but which are novel and important because of the presencetherein of a synergistic composition.

The formulations that are applied most often are aqueous suspensions oremulsions. Either such water-soluble, water-suspendable, or emulsifiableformulations are solids, usually known as wettable powders, or liquids,usually known as emulsifiable concentrates, aqueous suspensions, orsuspension concentrates. The present invention contemplates all vehiclesby which the synergistic compositions can be formulated for delivery anduse as a fungicide.

As will be readily appreciated, any material to which these synergisticcompositions can be added may be used, provided they yield the desiredutility without significant interference with the activity of thesesynergistic compositions as antifungal agents.

Wettable powders, which may be compacted to form water-dispersiblegranules, comprise an intimate mixture of the synergistic composition, acarrier and agriculturally acceptable surfactants. The concentration ofthe synergistic composition in the wettable powder is usually from about10% to about 90% by weight, more preferably about 25% to about 75% byweight, based on the total weight of the formulation. In the preparationof wettable powder formulations, the synergistic composition can becompounded with any of the finely divided solids, such as prophyllite,talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch,casein, gluten, montmorillonite clays, diatomaceous earths, purifiedsilicates or the like. In such operations, the finely divided carrier isground or mixed with the synergistic composition in a volatile organicsolvent. Effective surfactants, comprising from about 0.5% to about 10%by weight of the wettable powder, include sulfonated lignins,naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, andnon-ionic surfactants, such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of the synergistic composition comprise aconvenient concentration, such as from about 10% to about 50% by weight,in a suitable liquid, based on the total weight of the emulsifiableconcentrate formulation. The components of the synergistic compositions,jointly or separately, are dissolved in a carrier, which is either awater-miscible solvent or a mixture of water-immiscible organicsolvents, and emulsifiers. The concentrates may be diluted with waterand oil to form spray mixtures in the form of oil-in-water emulsions.Useful organic solvents include aromatics, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as, for example,terpenic solvents, including rosin derivatives, aliphatic ketones, suchas cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.

Emulsifiers which can be advantageously employed herein can be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulfonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which can be employed in preparing theemulsifiable concentrates of the present invention are the aromaticliquids such as xylene, propyl benzene fractions, or mixed naphthalenefractions, mineral oils, substituted aromatic organic liquids such asdioctyl phthalate, kerosene, dialkyl amides of various fatty acids,particularly the dimethyl amides of fatty glycols and glycol derivativessuch as the n-butyl ether, ethyl ether or methyl ether of diethyleneglycol, and the methyl ether of triethylene glycol. Mixtures of two ormore organic liquids are also often suitably employed in the preparationof the emulsifiable concentrate. The preferred organic liquids arexylene, and propyl benzene fractions, with xylene being most preferred.The surface-active dispersing agents are usually employed in liquidformulations and in the amount of from 0.1 to 20 percent by weight ofthe combined weight of the dispersing agent with the synergisticcompositions. The formulations can also contain other compatibleadditives, for example, plant growth regulators and other biologicallyactive compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds, dispersed in an aqueous vehicle at a concentration in therange from about 5% to about 70% by weight, based on the total weight ofthe aqueous suspension formulation. Suspensions are prepared by finelygrinding the components of the synergistic combination either togetheror separately, and vigorously mixing the ground material into a vehiclecomprised of water and surfactants chosen from the same types discussedabove. Other ingredients, such as inorganic salts and synthetic ornatural gums, may also be added to increase the density and viscosity ofthe aqueous vehicle. It is often most effective to grind and mix at thesame time by preparing the aqueous mixture and homogenizing it in animplement such as a sand mill, ball mill, or piston-type homogenizer.

The synergistic composition may also be applied as a granularformulation, which is particularly useful for applications to the soil.Granular formulations usually contain from about 0.5% to about 10% byweight of the compounds, based on the total weight of the granularformulation, dispersed in a carrier which consists entirely or in largepart of coarsely divided attapulgite, bentonite, diatomite, clay or asimilar inexpensive substance. Such formulations are usually prepared bydissolving the synergistic composition in a suitable solvent andapplying it to a granular carrier which has been preformed to theappropriate particle size, in the range of from about 0.5 to about 3 mm.Such formulations may also be prepared by making a dough or paste of thecarrier and the synergistic composition, and crushing and drying toobtain the desired granular particle.

Dusts containing the synergistic composition are prepared simply byintimately mixing the synergistic composition in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1% to about 10% by weight of the synergistic composition/carriercombination.

The formulations may contain agriculturally acceptable adjuvantsurfactants to enhance deposition, wetting and penetration of thesynergistic composition onto the target crop and organism. Theseadjuvant surfactants may optionally be employed as a component of theformulation or as a tank mix. The amount of adjuvant surfactant willvary from 0.01 percent to 1.0 percent volume/volume (v/v) based on aspray-volume of water, preferably 0.05 to 0.5 percent. Suitable adjuvantsurfactants include ethoxylated nonyl phenols, ethoxylated synthetic ornatural alcohols, salts of the esters or sulfosuccinic acids,ethoxylated organosilicones, ethoxylated fatty amines and blends ofsurfactants with mineral or vegetable oils.

The formulations may optionally include combinations that can compriseat least 1% by weight of one or more of the synergistic compositionswith another pesticidal compound. Such additional pesticidal compoundsmay be fungicides, insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the synergistic compositions of the present invention inthe medium selected for application, and not antagonistic to theactivity of the present compounds. Accordingly, in such embodiments theother pesticidal compound is employed as a supplemental toxicant for thesame or for a different pesticidal use. The pesticidal compound and thesynergistic composition can generally be mixed together in a weightratio of from 1:100 to 100:1.

The present invention includes within its scope methods for the controlor prevention of fungal attack. These methods comprise applying to thelocus of the fungus, or to a locus in which the infestation is to beprevented (for example applying to wheat or barley plants), afungicidally effective amount of the synergistic composition. Thesynergistic composition is suitable for treatment of various plants atfungicidal levels, while exhibiting low phytotoxicity. The synergisticcomposition is useful in a protectant or eradicant fashion. Thesynergistic composition is applied by any of a variety of knowntechniques, either as the synergistic composition or as a formulationcomprising the synergistic composition. For example, the synergisticcompositions may be applied to the roots, seeds or foliage of plants forthe control of various fungi, without damaging the commercial value ofthe plants. The synergistic composition is applied in the form of any ofthe generally used formulation types, for example, as solutions, dusts,wettable powders, flowable concentrates, or emulsifiable concentrates.These materials are conveniently applied in various known fashions.

The synergistic composition has been found to have significantfungicidal effect, particularly for agricultural use. The synergisticcomposition is particularly effective for use with agricultural cropsand horticultural plants, or with wood, paint, leather or carpetbacking.

In particular, the synergistic composition is effective in controlling avariety of undesirable fungi that infect useful plant crops. Thesynergistic composition may be used against a variety of Ascomycete andBasidiomycete fungi, including for example the following representativefungi species: wheat brown rust (Puccinia recondita; Bayer code PUCCRT);stripe rust of wheat (Puccinia striiformis; Bayer code PUCCST); leafblotch of wheat (Mycosphaerella graminicola; anamorph: Septoria tritici;Bayer code SEPTTR); glume blotch of wheat (Leptosphaeria nodorum; Bayercode LEPTNO; anamorph: Stagonospora nodorum); spot blotch of barley(Cochliobolus sativum; Bayer code COCHSA; anamorph: Helminthosporiumsativum); leaf spot of sugar beets (Cercospora beticola; Bayer codeCERCBE); leaf spot of peanut (Mycosphaerella arachidis; Bayer codeMYCOAR; anamorph: Cercospora arachidicola); cucumber anthracnose(Glomerella lagenarium; anamorph: Colletotrichum lagenarium; Bayer codeCOLLLA) and black sigatoka disease of banana (Mycosphaerella fijiensis;BAYER code MYCOFI). It will be understood by those in the art that theefficacy of the synergistic compositions for one or more of theforegoing fungi establishes the general utility of the synergisticcompositions as fungicides.

The synergistic compositions have a broad range of efficacy as afungicide. The exact amount of the synergistic composition to be appliedis dependent not only on the relative amounts of the components, butalso on the particular action desired, the fungal species to becontrolled, and the stage of growth thereof, as well as the part of theplant or other product to be contacted with the synergistic composition.Thus, formulations containing the synergistic composition may not beequally effective at similar concentrations or against the same fungalspecies.

The synergistic compositions are effective in use with plants in adisease-inhibiting and phytologically acceptable amount. The term“disease-inhibiting and phytologically acceptable amount” refers to anamount of the synergistic composition that kills or inhibits the plantdisease for which control is desired, but is not significantly toxic tothe plant. The exact concentration of synergistic composition requiredvaries with the fungal disease to be controlled, the type of formulationemployed, the method of application, the particular plant species,climate conditions, and the like.

The present compositions can be applied to fungi or their locus by theuse of conventional ground sprayers, granule applicators, and by otherconventional means known to those skilled in the art.

The following examples are provided to further illustrate the invention.They are not meant to be construed as limiting the invention.

Examples

Evaluation of Curative and Protectant Activity of Fungicide Mixtures vs.Leaf Blotch of Wheat (Mycosphaerella graminicola; Anamorph: Septoriatritici; Bayer Code: SEPTTR)

Wheat plants (variety Yuma) were grown from seed in a greenhouse inplastic pots with a surface area of 27.5 square centimeters (cm²)containing 50% mineral soil/50% soil-less Metro mix, with 8-12 seedlingsper pot. The plants were employed for testing when first leaf was fullyemerged, which typically took 7 to 8 days after planting. Test plantswere inoculated with an aqueous spore suspension of Septoria triticieither 3 days prior to (3-day curative test) or 1 day after fungicidetreatments (1-day protectant test). After inoculation the plants werekept in 100% relative humidity (one day in a dark dew chamber followedby two days in a lighted mist chamber) to permit spores to germinate andinfect the leaf. The plants were then transferred to a greenhouse fordisease to develop.

Evaluation of Curative Activity of Fungicide Mixtures vs. Wheat BrownRust (Puccinia recondita; Bayer Code: PUCCRT)

Yuma wheat seedlings were grown as described above, and inoculated withan aqueous spore suspension of Puccinia recondita 3 days prior to or1-day after fungicide treatment. After inoculation, plants were kept in100% relative humidity for 24 hours in a dark dew room to allow sporesto germinate and infect plants. The plants were then transferred to agreenhouse for disease to develop.

Treatments consisted of fungicides compound I, II, III, IV, V,epoxiconazole, prothioconazole, azoxystrobin, pyraclostrobin,penthiopyrad, boscalid, prochloraz, and chlorothalonil, either usingindividually or as two-way mixture with compounds I-V. For compound I,isopyrazam and bixafen were also included in the studies. Technicalgrades of materials were dissolved in acetone to make stock solutions,which were then used to perform dilutions in acetone either for eachindividual fungicide component or for the two-way mixture. Desiredfungicide rates were obtained after mixing dilutions with 9 volumes ofwater containing 110 parts per million (ppm) Triton X-100. Twentymilliliter (mL) fungicide solutions were applied onto 12 pots of plantsusing an automated booth sprayer, which utilized two 6218-1/4 JAUPMspray nozzles operating at 20 pounds per square inch (psi) set atopposing angles to cover both leaf surfaces. All sprayed plants wereallowed to air dry prior to further handling. Control plants weresprayed in the same manner with the solvent blank.

When disease fully developed on the control plants, infection levelswere assessed on treated plants visually and scored on a scale of 0 to100 percent. Percentage of disease control was then calculated using theratio of disease on treated plants relative to control plants.

Colby's equation was used to determine the fungicidal effects expectedfrom the mixtures. (See Colby, S. R. Calculation of the synergistic andantagonistic response of herbicide combinations. Weeds 1967, 15, 20-22.)

The following equation was used to calculate the expected activity ofmixtures containing two active ingredients, A and B:

Expected=A+B−(A×B/100)

A=observed efficacy of active component A at the same concentration asused in the mixture;B=observed efficacy of active component B at the same concentration asused in the mixture.

Representative synergistic interactions are presented in the followingTables 1-12.

% DC Obs=Percent disease control observed

% DC Exp=Percent disease control expected

Synergism factor=% DC Obs/% DC Exp

TABLE 1 Synergistic interactions of compound I and other fungicides in3-day curative (3DC) Septoria tritici (SEPTTR) tests % % DC DC SynergismRate ppm obs exp factor Compound I + epoxiconazole 0.4 + 0.1 71 43 1.64Compound I + epoxiconazole 0.15 + 0.13 97 48 2.02 Compound I +prothioconazole 0.4 + 25  99 72 1.38 Compound I + prothioconazole 1.35 +1.8  99 83 1.19 Compound I + prothioconazole 0.45 + 0.6  69 7 10.50Compound I + azoxystrobin 6.25 + 0.4  100 89 1.12 Compound I +azoxystrobin 1.35 + 2.25 99 83 1.19 Compound I + azoxystrobin 0.45 +0.75 72 15 4.78 Compound I + pyraclostrobin 0.1 + 0.4 92 80 1.15Compound I + penthiopyrad 6.25 + 0.1  98 90 1.08 Compound I +penthiopyrad 0.15 + 0.2  31 4 7.08 Compound I + isopyrazam 6.25 + 0.1 99 89 1.11 Compound I + isopyrazam  0.4 + 6.25 68 55 1.23 Compound I +isopyrazam  0.1 + 6.25 86 57 1.50

TABLE 2 Synergistic interactions of compound I and other fungicides in1-day protectant (1DP) SEPTTR tests % % DC DC Synergism Rate ppm obs expfactor Compound I + epoxiconazole 0.1 + 0.1 92 74 1.24 Compound I +epoxiconazole  0.1 + 0.025 85 55 1.53 Compound I + prothioconazole 0.1 + 1.56 94 70 1.34 Compound I + prothioconazole 0.15 + 0.2  46 153.01 Compound I + azoxystrobin  0.1 + 1.56 91 66 1.38 Compound I +azoxystrobin 0.1 + 0.4 72 43 1.66 Compound I + azoxystrobin 0.1 + 0.1 8061 1.31 Compound I + pyraclostrobin 0.1 + 0.1 99 92 1.08 Compound I +pyraclostrobin 0.05 + 0.08 68 30 2.27 Compound I + penthiopyrad 0.4 +0.4 96 90 1.07 Compound I + penthiopyrad 0.1 + 0.4 56 47 1.19 CompoundI + isopyrazam 0.15 + 0.13 49 9 5.68 Compound I + bixafen 0.15 + 0.2  3012 2.50 Compound I + boscalid 0.15 + 0.33 25 14 1.81 Compound I +prochloraz 0.15 + 0.45 35 7 5.00 Compound I + chlorothalonil 0.15 + 0.6 16 9 1.83

TABLE 3 Synergistic interactions of compound I and other fungicides in3DC Puccinia recondita (PUCCRT) tests % % DC DC Synergism Rate ppm obsexp factor Compound I + epoxiconazole 0.4 + 0.1 100 87 1.15 Compound I +epoxiconazole 0.1 + 0.1 100 82 1.22 Compound I + prothioconazole  0.4 +1.56 100 91 1.10 Compound I + prothioconazole 1.35 + 1.8  94 39 2.43Compound I + azoxystrobin 0.4 + 0.4 90 84 1.07 Compound I + azoxystrobin0.15 + 0.25 43 14 3.14 Compound I + pyraclostrobin 0.4 + 0.1 74 55 1.34Compound I + pyraclostrobin 0.1 + 0.4 74 64 1.15 Compound I + isopyrazam 0.4 + 1.56 100 95 1.05 Compound I + isopyrazam 0.45 + 0.38 33 29 1.13

TABLE 4 Synergistic interactions of compound I and other fungicides in1DP PUCCRT tests % % DC DC Synergism Rate ppm obs exp factor CompoundI + prothioconazole 0.15 + 0.2  78 69 1.14 Compound I + prochloraz0.15 + 0.45 93 69 1.35

TABLE 5 Synergistic interactions of compound II and other fungicides in1DP SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundII + epoxiconazole 0.45 + 0.2 54 33 1.67 Compound II + pyraclostrobin0.45 + 0.1 80 61 1.32 Compound II + boscalid 0.45 + 5   44 21 2.04Compound II + prochloraz 0.45 + 5   55 36 1.54

TABLE 6 Synergistic interactions of compound II and other fungicides 3DCSEPTTR tests % % DC DC Synergism Rate ppm obs exp factor Compound II +prothioconazole 1.35 + 1.8  95 38 2.49 Compound II + prothioconazole0.45 + 0.6  38 14 2.65 Compound II + azoxystrobin 1.35 + 2.25 98 72 1.36Compound II + azoxystrobin 0.45 + 0.75 71 52 1.36 Compound II +pyraclostrobin 0.15 + 0.25 95 50 1.89 Compound II + pyraclostrobin0.05 + 0.08 29 16 1.78 Compound II + boscalid 1.35 + 3   100 57 1.75Compound II + boscalid 0.45 + 1   60 22 2.73 Compound II + prochloraz1.35 + 4.05 95 53 1.81 Compound II + prochloraz 1.5 + 3   75 63 1.20Compound II + chlorothalonil 1.35 + 5.4  92 42 2.17 Compound II +chlorothalonil 0.45 + 1.8  58 18 3.22

TABLE 7 Synergistic interactions of compound III and other fungicides in1DP SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundIII + epoxiconazole 0.3 + 0.2 61 36 1.69 Compound III + prothioconazole1.35 + 1.8  98 90 1.09 Compound III + azoxystrobin 0.15 + 0.25 38 271.42 Compound III + pyraclostrobin 0.3 + 0.1 76 63 1.21 Compound III +penthiopyrad 0.3 + 3   53 42 1.25 Compound III + penthiopyrad 1.35 +1.8  95 89 1.07 Compound III + boscalid 1.35 + 3   97 91 1.07 CompoundIII + boscalid 0.3 + 5   56 25 2.22 Compound III + prochloraz 1.35 +4.05 98 91 1.07 Compound III + prochloraz 0.3 + 5   62 39 1.60 CompoundIII + chlorothalonil 1.35 + 5.4  95 86 1.11 Compound III +chlorothalonil 0.15 + 0.6  40 21 1.93

TABLE 8 Synergistic interactions of compound III and other fungicides in3DC SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundIII + epoxiconazole  0.5 + 0.03 73 60 1.21 Compound III +prothioconazole 0.45 + 0.6  88 33 2.69 Compound III + prothioconazole0.15 + 0.2  50 42 1.20 Compound III + azoxystrobin 0.45 + 0.75 95 631.51 Compound III + azoxystrobin 0.15 + 0.25 63 43 1.44 Compound III +pyraclostrobin  0.5 + 0.15 75 56 1.33 Compound III + penthiopyrad 0.45 +0.6  97 69 1.41 Compound III + boscalid 0.45 + 1   83 39 2.13 CompoundIII + boscalid 0.15 + 0.33 35 29 1.23 Compound III + prochloraz 0.45 +1.35 71 42 1.68 Compound III + prochloraz 0.15 + 0.45 67 22 3.08Compound III + chlorothalonil 0.45 + 1.8  58 36 1.62

TABLE 9 Synergistic interactions of compound IV and other fungicides in1DP SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundIV + epoxiconazole   2 + 0.2 42 37 1.14 Compound IV + prothioconazole4.2 + 5.6 90 78 1.15 Compound IV + boscalid 2 + 5 31 26 1.19 CompoundIV + chlorothalonil  4.2 + 16.8 84 67 1.26 Compound IV + chlorothalonil1.35 + 5.4  33 23 1.44

TABLE 10 Synergistic interactions of compound IV and other fungicides in3DC SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundIV + prothioconazole 4.2 + 5.6 97 64 1.52 Compound IV + azoxystrobin4.2 + 7   96 84 1.14 Compound IV + azoxystrobin 1.35 + 2.25 70 57 1.23Compound IV + pyraclostrobin   6 + 0.15 97 62 1.56 Compound IV +pyraclostrobin 0.05 + 0.08 30 22 1.40 Compound IV + penthiopyrad 4.2 +5.6 98 81 1.21 Compound IV + penthiopyrad 1.35 + 1.8  74 15 4.86Compound IV + boscalid 1.35 + 3   65 52 1.25 Compound IV + prochloraz6 + 3 72 63 1.15 Compound IV + chlorothalonil  4.2 + 16.8 67 10 7.05

TABLE 11 Synergistic interactions of compound V and other fungicides in1DP SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundV + epoxiconazole   2 + 0.2 97 87 1.11 Compound V + epoxiconazole 0.15 +0.13 28 17 1.61 Compound V + prothioconazole 0.45 + 0.6  20 14 1.39Compound V + azoxystrobin 0.45 + 0.75 38 12 3.09 Compound V +pyraclostrobin   2 + 0.1 99 93 1.07 Compound V + pyraclostrobin 0.05 +0.08 50 17 3.00 Compound V + penthiopyrad 0.45 + 0.6  23 14 1.56Compound V + boscalid 2 + 5 92 85 1.09 Compound V + prochloraz 1.35 +4.05 87 38 2.28 Compound V + prochloraz 0.45 + 1.35 38  5 7.23 CompoundV + chlorothalonil 1.35 + 5.4  57 25 2.26

TABLE 12 Synergistic interactions of compound V and other fungicides in3DC SEPTTR tests % % Rate DC DC Synergism ppm obs exp factor CompoundV + epoxiconazole   2 + 0.03 61 44 1.41 Compound V + prothioconazole1.35 + 1.8  78 52 1.51 Compound V + pyraclostrobin   2 + 0.15 86 38 2.30Compound V + penthiopyrad 2 + 1 50 33 1.50 Compound V + penthiopyrad1.35 + 1.8  67 37 1.81 Compound V + boscalid 2 + 2 50 41 1.22 CompoundV + prochloraz 2 + 3 56 38 1.45 Compound V + prochloraz 0.15 + 0.45 5040 1.26 Compound V + chlorothalonil  4.2 + 16.8 97 71 1.38 Compound V +chlorothalonil 1.35 + 5.4  54 34 1.59

For all tables, % DC=% Disease Control

1. A synergistic fungicidal mixture comprising a fungicidally effectiveamount of a compound of Formula II-V and a second fungicide selectedfrom the group consisting of epoxiconazole, prothioconazole,azoxystrobin, pyraclostrobin, penthiopyrad, isopyrazam, bixafen,boscalid, prochloraz and chlorothalonil, wherein the weight ratio of thecompound of Formula I-V to the second fungicide is between from about1:10 to about 10:1 when the second fungicide is selected from the groupconsisting of: prothioconazole, azoxvstrobin, pyraclostrobin,penthiopvrad, isopyrazam, bixafen, boscalid, and procloraz and fromabout 1:50 to about 1:1 when the second fungicide is chlorothalonil

2-11. (canceled)
 12. A fungicidal composition comprising a fungicidallyeffective amount of the fungicidal mixture of claim 1 and anagriculturally acceptable adjuvant or carrier.
 13. The mixture of claim1, wherein the compound of Formula II-V is selected from the groupconsisting of: the compound of Formula IV and the compound of Formula V.14. The mixture of claim 13, wherein the compound of Formula II-V is thecompound of Formula IV.
 15. The mixture of claim 1, wherein the compoundof Formula II-V is selected from the group consisting of: the compoundof Formula II and the compound of Formula III.
 16. The mixture of claim1, wherein the second fungicide is selected from the group consistingof: azoxystrobin, pyraclostrobin, penthiopyrad, isopyrazam, bixafen,boscalid, prochloraz, and chlorothalonil.
 17. The mixture of claim 16,wherein the second fungicide is pyraclostrobin.
 18. The mixture of claim1 in which the application rate of epoxiconazole is between about 30grams per hectare and about 125 grams per hectare and the applicationrate of the compound of Formula II-V is between about 35 grams perhectare and about 300 grams per hectare.
 19. The mixture of claim 1 inwhich the application rate of prothioconzaole is between about 50 gramsper hectare and about 200 grams per hectare and the application rate ofthe compound of Formula II-V is between about 35 grams per hectare andabout 300 grams per hectare.
 20. The mixture of claim 1 in which theapplication rate of azoxystrobin is between about 50 grams per hectareand about 250 grams per hectare and the application rate of the compoundof Formula II-V is between about 35 grams per hectare and about 300grams per hectare.
 21. The mixture of claim 1 in which the applicationrate of pyraclostrobin is between about 50 grams per hectare and about250 grams per hectare and the application rate of the compound ofFormula II-V is between about 35 grams per hectare and about 300 gramsper hectare.
 22. The mixture of claim 1 in which the application rate ofpenthiopyrad is between about 50 grams per hectare and about 300 gramsper hectare and the application rate of the compound of Formula II-V isbetween about 35 grams per hectare and about 300 grams per hectare. 23.The mixture of claim 1 in which the application rate of isopyrazam isbetween about 30 grams per hectare and about 125 grams per hectare andthe application rate of the compound of Formula II is between about 35grams per hectare and about 300 grams per hectare.
 24. The mixture ofclaim 1 in which the application rate of bixafen is between about 30grams per hectare and about 125 grams per hectare and the applicationrate of the compound of Formula II is between about 35 grams per hectareand about 300 grams per hectare.
 25. The mixture of claim 1 in which theapplication rate of boscalid is between about 50 grams per hectare andabout 350 grams per hectare and the application rate of the compound ofFormula II-V is between about 35 grams per hectare and about 300 gramsper hectare.
 26. The mixture of claim 1 in which the application rate ofprochloraz is between about 50 grams per hectare and about 450 grams perhectare and the application rate of the compound of Formula II-V isbetween about 35 grams per hectare and about 300 grams per hectare. 27.The mixture of claim 1 in which the application rate of chlorothalonilis between about 100 grams per hectare and about 2000 grams per hectareand the application rate of the compound of Formula II-V is betweenabout 35 grams per hectare and about 300 grams per hectare.
 28. Themixture of claim 1 in which the application rate of the mixture ifbetween about 65 grams per hectare and about 2300 grams per hectare.